1. Field of the Invention
The invention relates to new oil- and water-repellent papers which are treated on the surface or in the pulp with the fluorine-containing copolymers described below and to their production. The invention furthermore relates to new fluorine-containing copolymers for this purpose.
2. Description of the Related Art
Fluorine-containing treatment compositions based on perfluoroalkylphosphate salts have disadvantages in the production of oil- and water-repellent papers. Thus, for example, ammonium mono- and bis-(N-ethylperfluorooctanesulphonamidoethyl) phosphate is only oil-repellent but not water-repellent and fails above all when used in hard water. Although the diethanolamine salt of mono- and bis-(1H, 1H, 2H, 2H-perfluoroalkyl) phosphates shows an oil- and water-repellent action when used on the surface of paper, only oil-repellent but no water-repellent properties are observed when used in the pulp.
Although fluorine-containing copolymers according to U.S. Pat. No. 4,366,299 already represent improvements over the abovementioned fluorine compounds, the content of solvents caused by their preparation is a disadvantage, since it necessitates particular safety precautions during application because of the very low flash point.
Fluorine-containing copolymers according to U.S. Pat. No. 5,247,008 and aqueous, solvent-free dispersions prepared therefrom can also be employed for oil- and water-repellent treatment of papers. However, acceptable results are achieved at best by treatment on the surface of the papers; when used in the pulp, in contrast, significantly poorer results are achieved.
This disadvantage manifests itself in a particularly serious manner when chemical pulp based on waste paper is employed.
There has therefore continued to be efforts to discover oil- and water-repellent papers which can be treated both on the surface and in the pulp of the papers by using fluorine-containing, solvent-free copolymer dispersions without developing the disadvantages described above, it being necessary to meet the following prerequisites:
It must be ensured that the treated papers have both oil- and water-repellent properties. PA1 The use of non-softened tap water during treatment of the papers should not lead to precipitates of the fluorine-containing copolymer dispersions or to losses of the oil- and water-repellent effect. PA1 The fluorine-containing copolymer dispersions to be employed according to the invention must lead to good effect both when employed on the paper surface and when employed in the pulp. PA1 It must be ensured that papers based on waste paper can be given an oil- and water-repellent treatment. PA1 a) acrylates containing perfluoroalkyl groups, of the formula EQU CH.sub.2 .dbd.CR.sup.1 --COO--X--C.sub.n F.sub.2n+1 (I), PA1 b) monomers of the formula EQU CH.sub.2 .dbd.CR.sup.2 --COO--R.sup.3 (II), PA1 c) monomers of the formula EQU CH.sub.2 .dbd.CR.sup.4 --COO--(CH.sub.2 CH.sub.2 O).sub.m --R.sup.5 (III), PA1 d) monomers of the formula EQU CH.sub.2 .dbd.CR.sup.6 --COO--CH.sub.2 CH.sub.2 --N(R.sup.7,R.sup.8) (IVa) PA1 or, in salt-like form, of the formula EQU [CH.sub.2 .dbd.CR.sup.6 --COO--CH.sub.2 CH.sub.2 --N(R.sup.7,R.sup.8,R.sup.9)].sup..sym. Y.sup..crclbar. (IVb) PA1 or, in N-oxidized form, of the formula ##STR2## and e) monomers of the formula EQU CH.sub.2 .dbd.CR.sup.10 CONHR.sup.11 (V) PA1 n denotes a number from 4 to 20, preferably from 6 to 16, or a mixture of various values of n and PA1 m denotes a number from 3 to 20 or a mixture of various values of m, PA1 X represents the formulae --(CH.sub.2).sub.o --, SO.sub.2 NR.sup.12 CH.sub.2 CHR.sup.13 -- or --O--(CH.sub.2).sub.o --, wherein o denotes a number from 1 to 4, PA1 R.sup.1, R.sup.2, R.sup.4, R.sup.6, R.sup.10 and R.sup.13 independently of one another denote hydrogen or methyl, PA1 R.sup.3, R.sup.7, R.sup.8, R.sup.9 and R.sup.12 independently of one another represent straight-chain or branched C.sub.1 -C.sub.4 -alkyl, PA1 R.sup.5 denotes hydrogen or straight-chain or branched C.sub.1 -C.sub.8 -alkyl and PA1 R.sup.11 denotes hydrogen or straight-chain or branched C.sub.1 -C.sub.12 -alkyl, benzyl, --CH.sub.2 OH, --CH.sub.2 OCH.sub.3, --CH.sub.2 OC.sub.4 H.sub.9, --(CH.sub.2).sub.3 N(CH.sub.3).sub.2 or --(CH.sub.2)N.sup..sym. (CH.sub.3).sub.3 Cl.sup..crclbar. and PA1 Y.sup..crclbar. denotes one equivalent of a 1- to 3-valent anion, PA1 a) 45-75% by weight of C.sub.n H.sub.2n+1 --X--OCO--CR.sup.1 =CH.sub.2, PA1 b) 10-50% by weight of CH.sub.2 .dbd.CH.dbd.CO.dbd.OR.sup.4 and/or CH.sub.2 .dbd.C(CH.sub.3)--CO--OR.sup.12, PA1 c) 4-30% by weight of CH.sub.2 .dbd.CR.sup.5 --COO--(CHR.sup.6 --CH.sub.2 O).sub.p --R.sup.7 and PA1 d) 1-15% by weight of CH.sub.2 .dbd.CR.sup.11 --COO--CH.sub.2 --CH.sub.2 --N(R.sup.8,R.sup.9) or [CH.sub.2 .dbd.CR.sup.11 --COO--CH.sub.2 CH.sub.2 --N(R.sup.8,R.sup.9,R.sup.10)].sup..sym. y.sup..crclbar. or ##STR3## wherein, in the formulae, X represents .paren open-st.CH.sub.2 .paren close-st..sub.m --SO.sub.2 --NR.sup.2 --CH.sub.2 --CHR.sup.3 -- or --O.paren open-st.CH.sub.2 .paren close-st..sub.m PA1 n denotes a number from 4 to 12 and PA1 m denotes a number from 1 to 4, PA1 R.sup.1, R.sup.3, R.sup.5, R.sup.6 and R.sup.11 independently of one another represent hydrogen or methyl, PA1 R.sup.2, R.sup.8, R.sup.9 and R.sup.10 independently of one another denote C.sub.1 -C.sub.4 -alkyl, PA1 R.sup.4 represents C.sub.1 -C.sub.22 -alkyl, PA1 R.sup.7 represents C.sub.1 -C.sub.8 -alkyl, PA1 R.sup.12 represents C.sub.2 -C.sub.22 -alkyl and PA1 Y.sup..crclbar. denotes one equivalent of a 1- to 3-valent anion, PA1 a) 50-90% by weight of acrylates containing perfluoroalkyl groups, of the formula EQU CH.sub.2 .dbd.CR.sup.1 --COO--X--C.sub.n F.sub.2n+1 (I), PA1 b) 1 to 35% by weight of monomers of the formula EQU CH.sub.2 .dbd.CR.sup.2 --COO--R.sup.3 (II) PA1 c) 3 to 20% by weight of monomers of the formula EQU CH.sub.2 .dbd.CR.sup.4 --COO--(CH.sub.2 CH.sub.2 O).sub.m --R.sup.5 (III) PA1 d) 1 to 20% by weight of monomers of the formula EQU CH.sub.2 .dbd.CR.sup.6 --COO--CH.sub.2 CH.sub.2 --N(R.sup.7,R.sup.8) (IVa) PA1 or, in salt-like form, of the formula EQU [CH.sub.2 .dbd.CR.sup.6 --COO--CH.sub.2 CH.sub.2 --N(R.sup.7,R.sup.8,R.sup.9)].sup..sym. Y.sup..crclbar. (IVb) PA1 or, in N-oxidized form, of the formula ##STR4## e) 0.5 to 10% by weight of monomers of the formula EQU CH.sub.2 .dbd.CR.sup.10 CONHR.sup.11 (V) PA1 n denotes a number from 4 to 20, preferably from 6 to 16, or a mixture of various values of n and PA1 m denotes a number from 3 to 20 or a mixture of various values of m, PA1 X represents the formulae --(CH.sub.2).sub.o --, SO.sub.2 NR.sup.12 CH.sub.2 CHR.sup.13 -- or --O--(CH.sub.2).sub.o --, wherein o denotes a number from 1 to 4, PA1 R.sup.1, R.sup.2, R.sup.4, R.sup.6, R.sup.10 and R.sup.13 independently of one another denote hydrogen or methyl, PA1 R.sup.3, R.sup.7, R.sup.8, R.sup.9 and R.sup.12 independently of one another represent straight-chain or branched C.sub.1 -C.sub.4 -alkyl, PA1 R.sup.5 denotes hydrogen or straight-chain or branched C.sub.1 -C.sub.8 -alkyl and PA1 R.sup.11 denotes hydrogen or straight-chain or branched C.sub.1 -C.sub.12 -alkyl, benzyl, --CH.sub.2 OH, --CH.sub.2 OCH.sub.3, --CH.sub.2 OC.sub.4 H.sub.9, --(CH.sub.2).sub.3 N(CH.sub.3).sub.2 or --(CH.sub.2)N.sup..sym. (CH.sub.3).sub.3 Cl.sup..crclbar. and PA1 Y.sup..crclbar. denotes one equivalent of a 1- to 3-valent anion.